18

1
 Earlier Topics

• Introduction to Cryogenic Engineering

• Properties of Cryogenic Fluids

• Properties of Materials at Cryogenic Temperature

• Gas Liquefaction and Refrigeration Systems

2
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Current Topic
Topic : Gas Separation
• Basics of Gas Separation
• Ideal Gas Separation System
• Properties of Mixtures and the Governing Laws
• Principles of Gas Separation
• Rectification and Plate Calculations

• The current topic will be covered in 7 to 10

lectures.

• Tutorials and assignments are included at the end

of each lecture.
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Outline of the Lecture
Topic : Gas Separation

• Basics of Gas Separation

• Gas Separation methods

• Ideal Gas Separation System

• Work requirement

4
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Introduction
• As mentioned earlier, cryogenic industry is huge
owing to the various applications of the
cryogens, both in liquid and gaseous states.

• For example, the use of inert gases like argon in

chemical and welding industries has increased in
the recent past.

• Liquid Nitrogen is used as precoolant in most of

the cryogenic systems. Also, cryogens like LOX,
LH2 are used in rocket propulsion.

5
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Introduction
• In the recent past, LH2 is being considered as a
fuel for an automobile.

• Production of Ammonia in RCF industry, requires

separation of purge gases like Nitrogen, Argon
and other inert gases at cryogenic temperatures.

• For most practical purposes, Air is considered as

a mixture of 78% N2 + 21% O2 + 1% Ar.

• The other ingredients are Helium, Neon, Krypton

etc. which occur in negligible quantities.
6
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Introduction
• Air is the raw material for the production of most
of the gases and the process of separation of
any gas mixture into its individual components is
called as Gas Separation.

• In other words, this topic “Gas Separation”

deals with separation of various gas mixtures
and their purification.

7
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Gas Separation
• Different techniques of gas separation commonly
used are

• Synthetic membranes

• Adsorption

• Absorption

• Cryogenic distillation

8
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Gas Separation
Membrane • Synthetic membranes
are the porous media
B B A BA which allow only a
A A B B
B B BA certain gas molecules to
A A B pass through.
Piston
• The membrane in the
A BA A figure allows only Gas A
ABB A
A
BA A to pass and hence the
B B A
A A separation occurs.
Gas Separation
• For example, a thin
sheet of palladium allows
H2 to pass through.
9
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Gas Separation
B B A B B B B • Adsorption is the physical
A A B AA A B processes in which only a
A B B B B B
B A A A A B certain kind of gas molecules
A B B A B A are adhered to the adsorbing
Adsorbate surface.

• The adsorbate in the figure

B B A B B A B adheres only Gas A to the
A B B AA A B surface and hence the
A B A B B B
B B A A B separation occurs.
A A A A A
A A A AA A
Adsorbate • For example, finely divided
Nickel adsorbs hydrogen on to
its surface.
10
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Gas Separation
• Absorption is a chemical process in which a
substance in one physical state is taken into
other substance at a different physical state.

• For example, liquids being absorbed by a solid or

gases being absorbed by a liquid.

• When an incoming stream containing CO2 is

passed through a solution of Sodium hydroxide,
the later absorbs the gas and hence decreases
the CO2 content in the outgoing stream.

• Hence, this chemical process helps in the

separation of the mixture.
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Gas Separation
• Distillation is a process of separation
based on the differences in the
volatilities (boiling points).
Qout, 77 K
B
• If the process of distillation occurs
A+B at cryogenic temperatures, it is
called as Cryogenic Distillation.
A
• The commercial production of gases
Qin, 90 K like O2, N2, Argon, Neon, Krypton &
Xenon is obtained by cryogenic
distillation of Liquid Air.

12
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Gas Separation
• The separation of a mixture can be done at both
room temperature and cryogenic temperature.

• For example in the case of Air, the following

processes are possible.
Air(300K)
Separation
Liquefaction
O2(300K) N2(300K)
LOX(90K) LN2(77K) LOX(90K) LN2(77K)
Cryogenic Separation Room Temp. Separation
13
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Gas Separation
• Some of the advantages of Cryogenic separation
over Room Temperature separation are

• The separation at lower temperatures is most

economical (explained in further slides).

• There is an increased difference in the boiling

points of the ingredients (explained in further
slides).

• A large quantities of the gas can be separated.

• A high purity of the gas can be obtained.

14
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Is Gas Mixing Reversible?
• Consider a closed chamber
A A AA BB B
A AA A BBBB
B filled with Gas A and Gas B as
A AA A BBB shown in the figure.
A AA B B BB

• Initially, the gases are

B B B A B BB
A A A B A A
separated by an impervious
B B B wall.
B B B B B
A A A A
• If the wall is removed, the
A A AA BB B
gases would mix.
B
A AA A BBBB
A AA A BBB • However, the replacement of
A AA B B BB
wall would not result in the
separation of gases.
15
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Gas Separation
• It is clear that the mixing of two different gases
is an irreversible process because unmixing or
separation of the mixture requires work input.

• The system in which all the processes are

reversible is called as an Ideal System.

• Although in reality such a system does not exist,

a system can be conceived to serve the required
purpose as explained in the next slide.

16
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
B B A B B B • Consider a closed
Tm, pm A
A A B A A
A B chamber filled with a
B B B B
B A A A A A mixture of Gas A and
p1a, p1b Gas B as shown.

• The temperature and

mixture pressure are
Tm and pm
respectively.

• The partial pressures

of Gas A and Gas B
are given by p1a and
p1b respectively.
17
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
B B A B B B • The chamber has two
Tm, pm A
A A B A A
A B frictionless opposing
B B B B
B A A A A A pistons made of semi –
p1a, p1b permeable membranes
as shown in the figure.

• As seen earlier, a semi

– permeable
membrane is a film
which allows only one
kind of gas to pass
through but not the
other.

18
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
B B A B B B • The left piston (red)
Tm, pm A
A A B A A
A B allows only the Gas A
B B B B
B A A A A A to pass through, but
p1a, p1b not the Gas B.

A
A B AB B • Similarly, the right
A B A B
piston (green) allows
A B A B B
A B
A A B A BB only the Gas B to pass
through, but not the
A A A A B B
Gas A.
A A A B B
A A AAA BBB • When both pistons are
A A A A B
moved inward, the
mixture is separated.
19
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
B B A B B B • Since the processes are
Tm, pm A
A A B A A
A B reversible, the system
B B B B
B A A A A A interacts with the
p1a, p1b surroundings to
maintain a constant
QR temperature.
WA A B AB B WB
A
A B A B
• The work of separation
A B A B B
AB BB is the work required to
A A B A
compress each gas
from p1a or p1b  pm
at a constant
temperature Tm.

20
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
B B A B B B • Since the left piston is
Tm, pm A
A A B A A
A B permeable to Gas A,
B B B B
B A A A A A the Gas A exerts no
p1a, p1b pressure on the left
piston.
QR
WA A B AB B WB • Similarly, the gas B
A
A B A B
exerts no pressure on
A B A B B
AB BB the right piston.
A A B A

A A A A B B
A A A B B • When both the pistons
A A AAA BBB are moved inward, the
A A A A B
mixture is separated
at constant Tm.
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
A A A A B B • The entire processes
Tm, pm A A A B B
are assumed to be
A A AAA BBB
A A A A B reversible.

• The process is
A
A B AB B reversed due to the
A B A B
difference in the
A B A B B
A B
A A B A BB concentrations of Gas
A and Gas B.

• Hence, the mixing of

the gases would move
the pistons away and
produce work.
22
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
A A A A B B • The Work produced in
Tm, pm A A A B B
this mixing process is
A A AAA BBB
A A A A B same as the Work
done to separate at
constant Tm.
QR
WA A B AB B WB • The final condition is a
A
A B A B
system with a mixture
A B A B B
AB BB of Gas A and B at pm
A A B A

B B A B B B
and Tm.
Tm, pm A
A A B A A
A B
B A
B B B B • Also, the partial
A A A A
p1a, p1b pressures of Gas A
and B are p1a and p1b.
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
Initial Final
B B A B B B A A A A B B
Tm, pm A A A A B B
A A B A A
A B A A AAA
B B B B BBB
B A A A A A A A A A B
p1a, p1b Tm, pm

Gas Const T
A p1a  pm
B p1b  pm
• In other words, thermodynamically each gas is
compressed reversibly and isothermally from
its partial pressure to the mixture pressure.
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
Initial Final
B B A B B B A A A A B B
Tm, pm A A A A B B
A A B A A
A B A A AAA
B B B B BBB
B A A A A A A A A A B
p1a, p1b Tm, pm

Gas Const T
A p1a  pm
B p1b  pm
• In order to understand the process of
compression, say for a Gas A, from p1a to pm,
the following analysis is done.
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• Let the mol. wt. of Gas A and Gas B be molwa
and molwb respectively.

• Number of moles of Gas A is given by na = ma / molwa

• Similarly, number of moles of Gas B is nb = mb / molwb

• Then total number of moles in the mixture nm is

nm= na + nb

ya = na / nm yb = nb / nm
• Then the ratios and are the
mole fractions of Gas A and Gas B respectively.

26
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
Initial Final
B B A B B B A A A A B B
Tm, pm A A A A B B
A A B A A
A B A A AAA
B B B B BBB
B A A A A A A A A A B
p1a, p1b Tm, pm
Vtot Va Vb

p1aVtot= na ℜTm p1bVtot= nbℜTm pmVa= na ℜTm pmVb= nbℜTm

( p1a + p1b )Vtot = ( na + nb ) ℜTm Va na

=
p1a + p1b =
pm Vb nb

• The volume occupied by the each of the gas is

directly proportional to its number of moles.
27
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• From the earlier lectures, the work requirement
for a unit mass of gas compressed isothermally is
given by −Wi
= Tm ( s1 − s2 ) − ( h1 − h2 )
m
• The net ideal work requirement of the separation
process is the sum of the ideal work requirement
by Gas A and Gas B.

• Mathematically, −Wi = ( −Wi ,a ) + ( −Wi ,b )

• Dividing the above equation −W −W −Wi ,b

by the mass of the mixture = +
i i ,a

mm mm mm
mm, we get
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
−Wi −Wi ,a −Wi ,b
= +
mm mm mm
• The total mass of mixture mm is the sum of mass
of Gas A and Gas B.

• Mathematically, we have m=
m ma + mb

• Rearranging the terms, we can write the above

equation as
−Wi  −Wi ,a   ma   −Wi ,b   mb 
=   +  
mm  ma   mm   mb   mm 
• Here, ma and mb are the mass of the Gas A and
Gas B respectively.
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
−Wi  −Wi ,a   ma   −Wi ,b   mb 
=   +  
mm  ma   mm   mb   mm 
• The work requirement for each of the individual
gas is given by the following equations.
−Wi ,a −Wi ,b
= Tm ( s1a − s2 a ) − ( h1a − h2 a ) = Tm ( s1b − s2b ) − ( h1b − h2b )
ma mb
• Substituting and rearranging, we get
  ma  
  ( ( s1a − s2 a ) − ( h1a − h2 a ) ) 
−Wi   mm  
= Tm  
mm  
 +  mb  ( ( s1b − s2b ) − ( h1b − h2b ) ) 
 m 
  m 
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
  ma  
  ( ( s1a − s2 a ) − ( h1a − h2 a ) ) 
−Wi   mm  
= Tm  
mm  
 +  b  ( ( s1b − s2b ) − ( h1b − h2b ) ) 
m
 m 
  m  
• It is clear that the work requirement decreases
with the decrease in the temperature.

• Hence, the separation of mixtures at the

cryogenic temperatures is most economical.

• The subscripts 1 and 2 denote the initial and the

final conditions respectively.
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
  ma  
  ( ( s1a − s2 a ) − ( h1a − h2 a ) ) 
−Wi   mm  
= Tm  
mm  
 +  b  ( ( s1b − s2b ) − ( h1b − h2b ) ) 
m
 m 
  m  
• It means that for each gas, s1 and h1 are at the
partial pressure before the separation. And s2
and h2 are at mixture pressure after the
separation of the mixture.

• For the sake of understanding, let us first

evaluate only entropy and enthalpy terms for
each of the gases.
32
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• For an ideal gas, the specific entropy s and
specific enthalpy h can be expressed as
s = c p ln T − R ln p + sr

=
h c pT + hr

• where, sr and hr are some reference values.

• Hence, s and h for Gas A are given by

s1a = c pa ln Tm − Ra ln p1a + sra =
h1a c paTm + hra

s2 a = c pa ln Tm − Ra ln p1a + sra =
h2 a c paTm + hra

33
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• The entropy and enthalpy term for Gas A is as
given below.
( ( s1a − s2a ) − ( h1a − h2a ) )
• Substituting, we get
(c pa ln Tm − Ra ln p1a + sra − c pa ln Tm + Ra ln pm − sra )
− ( c paTm + hra − c paTm − hra )

 pm 
( ( s1a − s2a ) − ( h1a − h2a ) ) =
Ra ln  
 p1a 
• Also, for Gas B  pm 
( ( s1b − s2b ) − ( h1b − h2b ) ) =
Rb ln  
 1b 
p
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
 pm  • Substituting, we
( ( s1a − s2a ) − ( h1a − h2a ) ) =
Ra ln   get the ideal
 p1a 
work
 pm 
( ( s1b − s2b ) − ( h1b − h2b ) ) =
Rb ln   requirement as
 1b 
p
  ma  
  ( ( s1a − s2 a ) − ( h1a − h2 a ) ) 
−Wi   mm  
= Tm  
mm  
 +  mb  ( ( s1b − s2b ) − ( h1b − h2b ) ) 
 m 
  m 
−Wi   ma   pm   mb   pm  
Tm    Ra ln  +  Rb ln   
mm   mm   p1a   mm   p1b  
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Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• Since the process occurs at constant volume Vm,
using an ideal gas equation we can write
pmVm= nmℜTm p1aVm= na ℜTm p1bVm= nbℜTm

• Dividing one over the other, we have

pmVm nmℜTm pmVm nmℜTm
= =
p1aVm na ℜTm p1bVm nbℜTm

pm nm 1 pm nm 1
= = = =
p1a na ya p1b nb yb
• Where ya and yb are the mole fractions of Gas A
and Gas B respectively.

36
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• The ideal gas equation can also be expressed in
terms of the mass of the gas as shown below.
pmVm= nmℜTm p1aVm= na ℜTm p1bVm= nbℜTm

mm ma mb
=
pmVm ℜTm =
p1aVm ℜTm =
p1bVm ℜTm
molwm molwa molwb

pmVm = mm RmTm p1aVm = ma RaTm p1bVm = mb RbTm

ℜ
• In general, Ra = = and ℜ 8.314 J / mol − K
molwa
• Here ℜ and R are the Universal Gas Constant
and Specific Gas Constant respectively.
37
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• From the earlier slide, using the ideal gas
equation in terms of the gas mass, we have
pmVm = mm RmTm p1aVm = ma RaTm p1bVm = mb RbTm

• Dividing one over the other, we have

pmVm mm RmTm pmVm mm RmTm
= =
p1aVm ma RaTm p1bVm mb RbTm

pm mm Rm 1 pm mm Rm 1
= = = =
p1a ma Ra ya p1b mb Rb yb

ma Ra mb Rb
= Rm ya = Rm yb
mm mm
38
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
pm 1 pm 1 ma Ra mb Rb
= = = Rm ya = Rm yb
p1a ya p1b yb mm mm

−Wi   ma   pm   mb   pm  
Tm    Ra ln  +  Rb ln   
mm   mm   p1a   mm   p1b  
• Substituting, we have
−Wi   1   1 
RmTm  ya ln   + yb ln    pmVm= mm RmTm= nmℜTm
mm   ya   yb  

−Wi   1   1 
=
ℜTm  ya ln   + yb ln   
nm   ya   yb  
39
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• The ideal work of separation per mole of mixture
(Gas A and Gas B) is given by
−Wi   1   1 
=
ℜTm  ya ln   + yb ln   
nm   ya   yb  

• On the similar lines, if the mixture is composed

of three different gases, say Gas A, Gas B and
Gas C, the ideal work of separation per mole of
mixture is given by

−Wi   1   1   1 
=
ℜTm  ya ln   + yb ln   + yc ln   
nm   ya   yb   yc  
40
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Ideal Separation System
• Generalizing the above equation for a mixture of
N constituents, we have
−Wi N  1 
= ℜTm ∑ y j ln  
nm y 
j =1  j
• where yj is the mole fraction of jth component.

• Similar to the Liquefaction systems, the Figure

of Merit (FOM) is defined as given below.
−Wi −Wi
nm mm
=
FOM =
−W −W
nm mm
41
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Summary
• Different techniques employed are Synthetic
membranes, Adsorption, Absorption and
distillation.

• The separation can be done at both room

temperature and cryogenic temperature.

• In an Ideal system all the processes are

reversible and the work requirement in an ideal
gas separation is called as an Ideal Work.

42
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Summary
• Ideal work requirement per mole of mixture to
separate a mixture with N constituents is given
by
−Wi N  1 
= ℜTm ∑ y j ln  
nm y 
j =1  j
• where yj is the mole fraction of jth component.

43
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
• A self assessment exercise is given after
this slide.

• Kindly asses yourself for this lecture.

44
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Self Assessment
1. Air is considered as a mixture of ________.
2. Thin sheet of palladium allows only __ to pass
through.
3. ________ is the processes in which only a
certain kind of gas molecules are adhered.
4. ___ is a chemical process for gas separation.
5. ______ separation is most economical.

45
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Self Assessment
6. In an ideal system, each gas is compressed from
its ____ to the ______.
7. In an ideal system (( s
1a − s2 a ) − ( h1a − h2 a ) ) is ______.
8. The Specific Gas constant for a Gas A (Ra) is
______.

46
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Answers
1. 78% N2 + 21% O2 + 1% Ar
2. Hydrogen
3. Adsorption
4. Absorption
5. Cryogenic
6. partial pressure, mixture pressure
7. G( ( s1a − s2 a ) − ( h1a − h2 a ) ) =
Ra ln ( pm / p1a )
8. FRa = ℜ / mola

47
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay
 Thank You!

48
Prof. M D Atrey, Department of Mechanical Engineering, IIT Bombay